CN117385381A - Membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 System and method for preparing formic acid through hydrogenation - Google Patents
Membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 System and method for preparing formic acid through hydrogenation Download PDFInfo
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- CN117385381A CN117385381A CN202311234450.2A CN202311234450A CN117385381A CN 117385381 A CN117385381 A CN 117385381A CN 202311234450 A CN202311234450 A CN 202311234450A CN 117385381 A CN117385381 A CN 117385381A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 210
- 239000001257 hydrogen Substances 0.000 title claims abstract description 205
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000012528 membrane Substances 0.000 title claims abstract description 169
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000926 separation method Methods 0.000 title claims abstract description 66
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 51
- 239000003345 natural gas Substances 0.000 title claims abstract description 51
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008878 coupling Effects 0.000 title claims description 10
- 238000010168 coupling process Methods 0.000 title claims description 10
- 238000005859 coupling reaction Methods 0.000 title claims description 10
- 238000000605 extraction Methods 0.000 title claims description 7
- 239000007789 gas Substances 0.000 claims abstract description 73
- 238000011084 recovery Methods 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000000872 buffer Substances 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012466 permeate Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000012465 retentate Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002737 fuel gas Substances 0.000 claims description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000000658 coextraction Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 172
- 239000001569 carbon dioxide Substances 0.000 description 86
- 229910002092 carbon dioxide Inorganic materials 0.000 description 86
- 239000012535 impurity Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical group [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/225—Multiple stage diffusion
- B01D53/226—Multiple stage diffusion in serial connexion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
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- C25B3/00—Electrolytic production of organic compounds
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- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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Abstract
The invention belongs to the technical field of chemical industry, and relates to a natural gas for hydrogen additionIs coupled with electrochemical hydrogen pump to extract hydrogen and CO 2 A system and a method for preparing formic acid by hydrogenation. Using two stages H 2 Membrane separation technology for recovering and concentrating H from hydrogen-doped natural gas 2 By electrochemical hydrogen pumps H 2 High-purity H for fuel cell automobile is prepared to separator high efficiency 2 And adjusting the hydrogen-carbon ratio of the dehydrogenation tail gas; by H 2 Separation membrane and CO 2 The separation membrane obtains the H-enriched gas in a 'first-stage two-stage' mode 2 And is rich in CO 2 Gas flow, simultaneous recovery of CH in dehydrogenation tail gas 4 . Rich in H 2 And is rich in CO 2 The gas flows respectively enter the electrochemical hydrogen pump CO 2 And preparing formic acid under the action of external voltage by using anode and cathode of hydrogenation equipment. The invention can realize the H of hydrogen-doped natural gas with high efficiency and low consumption 2 Recovery, H 2 /CO 2 Separation and CO 2 Efficient hydrogenation recycling method for preparing high-purity H for fuel cell automobile 2 CO is realized at the same time 2 The resource utilization has obvious economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 A method for preparing formic acid by hydrogenation.
Background
With the rapid development of fuel cell automobiles, low-impurity high-purity hydrogen (H 2 ) The demand for (c) increases substantially. H 2 Is an alternative energy source of a future power system, has the advantages of high mass energy density, high energy conversion efficiency, zero carbon emission and the like, and is a clean energy source with wide prospects in carbon peaks, carbon neutralization and background.
Hydrogen-loaded natural gas is a viable method for remote large-scale hydrogen transport, which contains large amounts of methane (CH) 4 ) More H 2 Ethane (C) 2 H 6 ) Propane (C) 3 H 8 ) Carbon dioxide (CO) 2 ) And the like. The direct use of hydrogen-doped natural gas as a household fuel can result in serious waste of hydrogen sources, and high-purity H for fuel cell automobiles is extracted from the hydrogen-doped natural gas 2 Is a reasonable scheme for realizing the high-efficiency utilization of the hydrogen-doped natural gas.
Use of commercial polymer membranes from low H 2 The concentration of hydrogen-doped natural gas for hydrogen recovery is limited by the current commercial polymer membrane H 2 /CO 2 Selectivity is generally not high, CO in natural gas pipelines 2 And H is 2 Together are enriched. Existing H 2 And CO 2 In the separation method, the methods of ammonia solution absorption, pressure swing adsorption and the like face the problems of high energy consumption, high operation cost and the like, and the electrochemical hydrogen pump is a novel hydrogen separation technology and provides a new solution for the efficient separation of hydrogen. At the same time, CO 2 Is also a large amount of basic chemical raw materials, can be converted into products with huge demands in the fields of chemical industry, food, medicine and the like through hydrogenation reaction, and realizes CO 2 And the method is used for recycling and reducing carbon emission.
The membrane separation is a separation technology based on the difference of gas molecular permeation rates, does not depend on the phase balance of a separation system, is an effective gas separation mode, and has been rapidly developed in recent decades due to the obvious advantages of small occupied area, simple operation, high separation efficiency, low investment and energy consumption and the like. Membrane separation techniques have been applied to purify H from various gas mixtures 2 And has the characteristic of high recovery rate. Meanwhile, the gas membrane separation technology has low operation difficulty and is easy to couple with other separation technologies.
The electrochemical hydrogen pump is a technology for separating hydrogen by utilizing electric drive, and provides a new solution for high-efficiency separation of hydrogen. Dissociation of anode-side hydrogen into H in electrochemical hydrogen pump + Under the action of external voltage, the electrons reach the cathode through the proton exchange membrane and are regenerated into H 2 Therefore, the method has the advantages of high hydrogen selectivity, low energy consumption in the separation process, no introduction of other impurities, small equipment occupation area and easy operation (continuous process), purification and compression are simultaneously carried out, and the method can be theoretically and directly transportedHigh-pressure high-purity hydrogen gas and the like, and has the advantages of environmental protection, no noise and no pollution. However, the noble metal catalyst on the membrane electrode is easily poisoned by impurities such as CO, and thus, there is a certain demand for a separation system. The membrane separation device is used for H 2 Performing primary concentration to remove most of impurities, and then purifying by an electrochemical hydrogen pump device to obtain high-purity H for fuel cell automobiles 2 The product can avoid the poisoning of catalyst by a large amount of CO and other impurities.
Electrochemical Hydrogen Pump CO 2 The hydrogenation device adopts an external voltage to activate chemically inert CO 2 CO reduction using gas diffusion electrodes and circulating electrolyte 2 The mass transfer resistance of (2) realizes CO at normal temperature and normal pressure 2 High-efficiency hydrogenation. Compared with high-temperature and high-pressure heterogeneous reactors such as fixed beds and fluidized beds, the high-temperature and high-pressure heterogeneous reactor has high safety and low energy consumption; CO activated at normal temperature with plasma radiation, H-type static electrolytic cell and the like 2 Compared with a hydrogenation device, the cost of equipment is lower, and CO 2 The mass transfer resistance is smaller.
H-enriched from membrane separation section 2 High-purity H for fuel cell automobile can be efficiently prepared by airflow through electrochemical hydrogen pump 2 The dehydrogenation tail gas contains a large amount of CO 2 And CH (CH) 4 Direct emissions which do not meet the green production objectives can also result in significant amounts of CH 4 Loss. Control of hydrogen to carbon ratio in dehydrogenation tail gas by adjusting electrochemical hydrogen pump operating parameters utilizing H 2 Separation membrane and CO 2 The separation membrane obtains the H-enriched gas in a 'first-stage two-stage' mode 2 And is rich in CO 2 Gas flow, simultaneous recovery of CH in dehydrogenation tail gas 4 . Rich in H 2 And is rich in CO 2 The gas flows respectively enter the electrochemical hydrogen pump CO 2 And preparing formic acid under the action of external voltage by using anode and cathode of hydrogenation equipment. The hydrogen extraction and the hydrogenation process complement each other, thereby realizing the efficient recycling utilization of the hydrogen-doped natural gas and CO 2 And emission reduction.
Disclosure of Invention
The invention aims to provide a method for extracting hydrogen and CO by coupling membrane separation and electrochemical hydrogen pump of hydrogen-doped natural gas 2 A method for preparing formic acid by hydrogenation. Hydrogen-loaded natural gas from low hydrogen concentration using a two-stage membrane separation processRecovering and concentrating H 2 High-purity H for fuel cell automobile is prepared efficiently through electrochemical hydrogen pump 2 . And the hydrogen-carbon ratio in the dehydrogenation tail gas is regulated by an electrochemical hydrogen pump, and H is utilized 2 Separation membrane and CO 2 The separation membrane obtains the H-enriched gas in a 'first-stage two-stage' mode 2 And is rich in CO 2 Gas flow, simultaneous recovery of CH in dehydrogenation tail gas 4 . Rich in H 2 And is rich in CO 2 The gas flows respectively enter the electrochemical hydrogen pump CO 2 And preparing formic acid under the action of external voltage by using anode and cathode of hydrogenation equipment. The invention can realize the recovery of hydrogen and H of the natural gas with low hydrogen concentration with high efficiency and low consumption 2 /CO 2 Separation and CO 2 High-efficiency hydrogenation recycling is carried out to obtain high-purity H for fuel cell automobiles 2 Simultaneous CO realization of products 2 The emission is reduced, the utilization is efficient, and obvious economic and environmental benefits are achieved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 The hydrogenation formic acid preparation system comprises a No. 1 compressor 1, a No. 1 heat exchanger 2, a No. 1 buffer tank 3, a No. 1 hydrogen membrane separator 4, a No. 2 compressor 5, a No. 2 heat exchanger 6, a No. 2 hydrogen membrane separator 7 and a No. 1 electrochemical hydrogen pump H 2 Separation device 8, 3# compressor 9, 3# heat exchanger 10, 2# buffer tank 11, 3# hydrogen membrane separator 12, 4# heat exchanger 13, 1# CO 2 Membrane separator 14, no. 5 heat exchanger 15, no. 1 electrochemical hydrogen pump CO 2 A hydrogenation unit 16, a 4# compressor 17, a 6# heat exchanger 18 and a 1# liquid separation tank 19.
The No. 1 compressor 1, the No. 1 heat exchanger 2 and the No. 1 buffer tank 3 are sequentially connected; the outlet of the No. 1 buffer tank 3 is connected with the inlet of the No. 1 hydrogen membrane separator 4, the permeation side of the No. 1 hydrogen membrane separator 4 is sequentially connected with the No. 2 compressor 5 and the No. 2 heat exchanger 6, the outlet of the No. 2 heat exchanger 6 is connected with the inlet of the No. 2 hydrogen membrane separator 7, and the permeation side of the No. 2 hydrogen membrane separator 7 is connected with the No. 1 electrochemical hydrogen pump H 2 The inlet of the separation device 8 is connected; the permeation side of the No. 2 hydrogen membrane separator 7 is connected with the No. 1 buffer tank 3; no. 1 electrochemical hydrogen Pump H 2 Separation device 8The 3 rd compressor 9, the 3 rd heat exchanger 10 and the 2 nd buffer tank 11 are sequentially connected after the anode side outlet; the outlet of the No. 2 buffer tank 11 is connected with the inlet of the No. 3 hydrogen membrane separator 12, and the retentate side of the No. 3 hydrogen membrane separator 12 is connected with the No. 1#CO 2 The inlet of the membrane separator 14 is connected; the permeation side of the No. 3 hydrogen membrane separator 12 is connected with a No. 4 heat exchanger 13, and the outlet of the No. 4 heat exchanger 13 is connected with a No. 1 electrochemical hydrogen pump CO 2 The anode inlet of the hydrogenation unit 16 is connected to the 1 st#CO 2 The permeation side of the membrane separator 14 is connected with a No. 5 heat exchanger 15, and the outlet of the No. 5 heat exchanger 15 is connected with a No. 1 electrochemical hydrogen pump CO 2 The cathode inlet of the hydrogenation unit 16 is connected with an electrochemical hydrogen pump CO No. 1 2 The anode outlet of the hydrogenation device 16 is sequentially connected with a No. 4 compressor 17, a No. 6 heat exchanger 18 and a No. 2 buffer tank 11, and a No. 1 electrochemical hydrogen pump CO 2 The cathode outlet of the hydrogenation device 16 is connected with a No. 1 liquid separating tank 19; retentate side of # 1 hydrogen membrane separator 4, # 1 CO 2 The residual seepage sides of the membrane separators 14 are connected with a natural gas pipeline;
membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 Method for preparing formic acid by hydrogenation, wherein the main component of hydrogen-doped natural gas is CH 4 、H 2 、C 2 H 6 、CO 2 And C 3 H 8 . First, the hydrogen-doped natural gas enters a No. 1 hydrogen membrane separator 4 to be enriched with H 2 H-rich on permeate side 2 The gas flow enters a No. 2 hydrogen membrane separator 7 to H 2 Performing primary concentration, and enriching CH on the residual side 4 The gas stream is returned to the natural gas pipeline for continued delivery to downstream natural gas end users. H-enriched permeate side of No. 2 hydrogen membrane separator 7 2 The gas flow enters a No. 1 electrochemical hydrogen pump H 2 High-purity H for fuel cell automobile prepared by separating device 8 2 The product, the residual side returns to the No. 1 buffer tank 3 for recycling to improve H 2 Recovery rate. No. 1 electrochemical hydrogen Pump H 2 The cathode side of the separation device 8 outputs high-purity hydrogen, and the dehydrogenation tail gas at the anode side sequentially enters a No. 3 hydrogen membrane separator 12 and a No. 1 CO after being compressed 2 Membrane separator 14 to obtain a H-rich stream 2 And is rich in CO 2 Gas flow and recovery of CH in dehydrogenation tail gas 4 . Rich in H 2 And is rich in CO 2 The air flows respectively enter the 1# electrochemicalHydrogen pump CO 2 The anode and cathode of the hydrogenation unit 16 are driven by an applied voltage to form an anode H 2 Dissociation to produce H + CO entering the surface of the cathode catalytic layer and the cathode through the proton exchange membrane and the buffer solution 2 React to generate formic acid, CO and H 2 O and H 2 . The cathode gas-liquid phase mixture enters a No. 1 liquid separating tank 19, formic acid solution and fuel gas are obtained after flash evaporation separation, the fuel gas can enter a hydrogen pipe network, and the formic acid solution is conveyed to an external device of the boundary region.
Further, the membrane separation and electrochemical hydrogen pump coupling hydrogen and CO extraction for hydrogen-doped natural gas 2 The hydrogenation formic acid preparation method specifically comprises the following steps:
h in the hydrogen-doped natural gas 2 The concentration is more than 5mol%, the mixture is pressurized to 2.0-5.0 MPa by a No. 1 compressor 1, the mixture is cooled to 40-80 ℃ by a No. 1 heat exchanger 2, and enters a No. 1 buffer tank 3 to be mixed with a circulating material flow from the permeation side of a No. 2 hydrogen membrane separator 7 in the No. 1 buffer tank 3, and enters a No. 1 hydrogen membrane separator 4 to be separated. The permeation side pressure of the No. 1 hydrogen membrane separator 4 is 0.1-0.5 MPa, the hydrogen in the gas at the membrane permeation side is initially concentrated, the hydrogen is pressurized to 2.0-5.0 MPa by the No. 2 compressor 5, cooled to 40-80 ℃ by the No. 2 heat exchanger 6, and enters the No. 2 hydrogen membrane separator 7 for further concentration. The residual gas from the No. 1 hydrogen membrane separator 4 is returned to the natural gas pipeline for further delivery to downstream natural gas end users. The permeation side pressure of the No. 2 hydrogen membrane separator 7 is 0.1-0.5 MPa, and the gas on the permeation side of the membrane is concentrated to H 2 The concentration is more than 80mol percent, and enters a No. 1 electrochemical hydrogen pump H 2 The separator 8 separates to obtain H on the cathode side 2 Purity of>99.97% CO purity<0.2ppm，CO 2 Purity of<2ppm，CH 4 Purity of<High purity H for fuel cell automobile of 2ppm (GB/T37244-2018) 2 And (5) a product. The gas on the retentate side of the No. 2 hydrogen membrane separator 7 is returned to the No. 1 buffer tank 3 for circulation to improve H 2 Recovery rate. No. 1 electrochemical hydrogen Pump H 2 The dehydrogenation tail gas at the anode side of the separation device 8 is compressed to 2.0-5.0 MPa by a No. 3 compressor 9, cooled to 40-80 ℃ by a No. 3 heat exchanger 10, enters a No. 2 buffer tank 11 and is mixed with the stream cooled by a No. 6 heat exchanger 18. The mixed gas enters a No. 3 hydrogen membraneSeparator 12, obtaining an H-rich permeate side 2 The air flow is cooled to 25-35 ℃ by a No. 4 heat exchanger 13 and then enters a No. 1 electrochemical hydrogen pump CO 2 Anode of hydrogenation unit 16. The residual gas of the No. 3 hydrogen membrane separator 12 enters No. 1#CO 2 Membrane separator 14, obtaining a CO-rich permeate side 2 The air flow is cooled to 25 to 35 ℃ by a No. 5 heat exchanger 15 and then enters a No. 1 electrochemical hydrogen pump CO 2 The cathode of hydrogenation unit 16. 1# CO 2 The retentate side gas from membrane separator 14 is returned to the natural gas pipeline for continued delivery to downstream natural gas end users. No. 1 electrochemical Hydrogen Pump CO 2 The external power supply of the hydrogenation device 16 adopts a constant voltage mode, the cathode potential range is 2.2-2.8V, and the catalyst is Ag/AgCl. Under the action of an applied voltage, the No. 1 electrochemical hydrogen pump CO 2 Hydrogen on the anode side of hydrogenation unit 16 dissociates into H + And pass through the proton exchange membrane and buffer solution to reach the cathode, and CO on the cathode side 2 And the reaction is efficient to prepare the formic acid. The anode outlet gas F is compressed to 2.0-5.0 MPa by a No. 4 compressor 17, enters a No. 6 heat exchanger 18 to be cooled to 40-80 ℃ and then enters a No. 2 buffer tank 11. The cathode gas-liquid phase mixture I enters a No. 1 liquid separating tank 19, and formic acid solution and fuel gas are obtained after flash evaporation separation.
The No. 1 hydrogen membrane separator 4, the No. 2 hydrogen membrane separator 7, the No. 3 hydrogen membrane separator 12 and the No. 1 CO 2 The membrane separator 14 may be hollow fiber membrane or flat plate membrane.
The hollow fiber membrane or the flat membrane is an organic membrane.
The No. 1 electrochemical hydrogen pump H 2 The separation device 8 is a low-temperature electrochemical hydrogen pump, the adopted catalyst is a platinum noble metal catalyst or a non-noble metal catalyst, the adopted proton exchange membrane material is a perfluorosulfonic acid proton exchange membrane or a non-fluorine proton exchange membrane, and the adopted gas diffusion layer material is carbon paper.
In the raw material hydrogen-doped natural gas, the hydrogen content is more than 5.0mol percent.
The No. 1 compressor 1, the No. 2 compressor 5, the No. 3 compressor 9 and the No. 4 compressor 17 adopted by the hydrogen separation and recovery system are reciprocating compressors, centrifugal compressors, axial compressors or screw compressors.
The No. 1 electrochemical hydrogen pump H 2 The hydrogen content of the high-purity hydrogen obtained on the cathode side of the separation device 8 is more than or equal to 99.97mol percent.
The No. 1 electrochemical hydrogen pump CO 2 The proton exchange membrane material used in the hydrogenation unit 16 is a perfluorosulfonic acid proton exchange membrane or a non-fluoroproton exchange membrane.
The No. 1 electrochemical hydrogen pump CO 2 CO of hydrogenation unit 16 2 The raw material can be CO contained in the hydrogen-doped natural gas 2 CO trapped in the out-of-limit region may be 2 。
The invention has the beneficial effects that: (1) Two-stage hydrogen membrane separation coupling electrochemical hydrogen pump H 2 The separation device can realize the efficient recovery and preparation of high-purity H for the fuel cell automobile from the hydrogen-doped natural gas with low hydrogen concentration 2 The product has obvious economic benefit and environmental benefit; (2) Electrochemical hydrogen pump for preparing high-purity H for fuel cell automobile 2 Can adjust the hydrogen-carbon ratio in the dehydrogenation tail gas and utilize H 2 Separation membrane and CO 2 The separation membrane obtains the H-enriched gas in a 'first-stage two-stage' mode 2 And is rich in CO 2 The air flow can remove the accumulation of inert gases in the coupling flow, realize the recycling of raw material gas and improve CO 2 Recovery of CH in dehydrogenation tail gas while conversion 4 The method comprises the steps of carrying out a first treatment on the surface of the (3) Rich in H 2 And is rich in CO 2 The gas flows respectively enter the electrochemical hydrogen pump CO 2 The anode and the cathode of the hydrogenation device can realize CO at normal temperature and normal pressure under the action of external voltage 2 Hydrogenation to obtain hydrogen fuel carrier formic acid, regulating reaction selectivity and CO by cathode potential 2 The conversion rate has the advantages of easy operation, controllable reaction and the like, and realizes CO with high efficiency and low consumption 2 And (5) recycling.
Drawings
FIG. 1 is a process flow diagram of an implementation of the present invention;
in the figure: 1 st compressor, 2 st heat exchanger, 3 st buffer tank, 4 st hydrogen membrane separator, 5 nd compressor, 6 nd heat exchanger, 7 nd hydrogen membrane separator, 8 st electrochemical hydrogen pump H 2 Separation device, 9 rd # 3 compressor,10 # 3 heat exchanger, 11 # 2 buffer tank, 12 # 3 hydrogen membrane separator, 13 # 4 heat exchanger, 14 # 1# CO 2 Membrane separator, 15 # 5 heat exchanger, 16 # 1 electrochemical hydrogen pump CO 2 A hydrogenation device, a No. 4 compressor 17, a No. 6 heat exchanger 18 and a No. 1 liquid separating tank 19.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Referring to FIG. 1, the system of the present invention comprises a # 1 compressor 1, a # 1 heat exchanger 2, a # 1 buffer tank 3, a # 1 hydrogen membrane separator 4, a # 2 compressor 5, a # 2 heat exchanger 6, a # 2 hydrogen membrane separator 7, a # 1 electrochemical hydrogen pump H, which are sequentially connected 2 Separation device 8, 3# compressor 9, 3# heat exchanger 10, 2# buffer tank 11, 3# hydrogen membrane separator 12, 4# heat exchanger 13, 1# CO 2 Membrane separator 14, no. 5 heat exchanger 15, no. 1 electrochemical hydrogen pump CO 2 A hydrogenation unit 16, a No. 4 compressor 17, a No. 6 heat exchanger 18, and a No. 1 liquid separation tank 19.
The hydrogen-doped natural gas contains 10mol% of H 2 Pressurizing to 3.0MPa by a No. 1 compressor 1, cooling to 80 ℃ by a No. 1 heat exchanger 2, mixing the circulating material flows from the permeation residue side of a No. 2 hydrogen membrane separator 7 in a No. 1 buffer tank 3 and a No. 1 buffer tank 3, and separating by a No. 1 hydrogen membrane separator 4. The No. 1 hydrogen membrane separator 4, the No. 2 hydrogen membrane separator 7 and the No. 3 hydrogen membrane separator 12 all adopt hollow fiber membrane structures, and the membrane material is Polyimide (PI) organic membranes. The permeation side pressure of the No. 1 hydrogen membrane separator 4 is 0.1MPa, hydrogen in the gas at the permeation side of the membrane is initially concentrated, the hydrogen is pressurized to 3.0MPa by the No. 2 compressor 5, cooled to 80 ℃ by the No. 2 heat exchanger 6, and enters the No. 2 hydrogen membrane separator 7 for further concentration. The residual gas from the No. 1 hydrogen membrane separator 4 is returned to the natural gas pipeline for further delivery to downstream natural gas end users. The permeate side pressure of the No. 2 hydrogen membrane separator 7 was 0.1MPa, and the membrane permeate side gas was concentrated to H 2 The concentration is more than 90mol percent, and enters a No. 1 electrochemical hydrogen pump H 2 The separation device 8 obtains H 2 Purity of>99.97% CO purity<0.2ppm，CO 2 Purity of<2ppm，CH 4 Purity of<2ppm (GB/T37244-2018) high purity H for product fuel cell automobile 2 And (5) a product. No. 1 electrochemical hydrogen Pump H 2 The separation device 8 is a low-temperature electrochemical hydrogen pump, and the operation temperature is 60 ℃; the catalyst is a platinum noble metal catalyst, and specifically is platinum carbon (Pt/C, the platinum content is 5%); the proton exchange membrane material is perfluorosulfonic acid proton exchange membrane, specifically Nafion 212; the gas diffusion layer material adopted is carbon paper, and is specifically HCP020N. The gas on the retentate side of the No. 2 hydrogen membrane separator 7 is returned to the No. 1 buffer tank 3 for recycling to improve H 2 Recovery rate. No. 1 electrochemical hydrogen Pump H 2 The high-purity hydrogen is output from the cathode side of the separation device 8, the dehydrogenation tail gas from the anode side is compressed to 3.0MPa by a No. 3 compressor 9, cooled to 80 ℃ by a No. 3 heat exchanger 10, enters a No. 2 buffer tank 11, and is mixed with the cooled stream from a No. 6 heat exchanger 18. The mixed gas G enters a No. 3 hydrogen membrane separator 12, the membrane permeation side pressure is 0.1MPa, and H-enriched gas is obtained at the permeation side 2 The air flow is cooled to 25 ℃ by a No. 4 heat exchanger 13 and then enters a No. 1 electrochemical hydrogen pump CO 2 Anode of hydrogenation unit 16. The residual gas of the No. 3 hydrogen membrane separator 12 enters No. 1#CO 2 A membrane separator 14, wherein the membrane permeation side pressure is 0.1MPa, and CO-enriched is obtained at the permeation side 2 The air flow is cooled to 25 ℃ by a No. 5 heat exchanger 15 and then enters a No. 1 electrochemical hydrogen pump CO 2 The cathode of hydrogenation unit 16. 1# CO 2 The membrane separator 14 adopts a hollow fiber membrane structure, and the membrane material is a polyvinyl amine (PVAm) organic membrane. 1# CO 2 The retentate side gas from membrane separator 14 is returned to the natural gas pipeline for continued delivery to downstream natural gas end users. No. 1 electrochemical Hydrogen Pump CO 2 The proton exchange membrane of the hydrogenation device 16 adopts a perfluorosulfonic acid proton exchange membrane, in particular Nafion117; the catalyst is Ag/AgCl; the applied voltage was 2.8V. H in anode feed gas under the action of external voltage 2 Dissociation to produce H + Enters the surface of the cathode catalytic layer through the proton exchange membrane and the buffer solution to be connected with CO in the cathode feed gas 2 React to form formic acid, CO and H 2 . KHCO buffer of 0.5mol/L 3 A solution. The anode outlet gas F is compressed to 3.0MPa by a No. 4 compressor 17, enters a No. 6 heat exchanger 18 and is cooled to 80 DEG CInto buffer tank # 2 11. The cathode gas-liquid phase mixture I enters a No. 1 liquid separating tank 19, and formic acid solution and fuel gas are obtained after separation. In this example, 1360.3kg H per hour can be obtained 2 And 611.9kg of formic acid, 449.4kg of CH can be recovered per hour 4 /H 2 Mixed gas, CO of whole flow 2 The utilization rate is 68.26%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. Membrane separation and electrochemical hydrogen pump coupling hydrogen extraction and CO for hydrogen-doped natural gas 2 The hydrogenation formic acid preparation system is characterized by comprising a No. 1 compressor (1), a No. 1 heat exchanger (2), a No. 1 buffer tank (3), a No. 1 hydrogen membrane separator (4), a No. 2 compressor (5), a No. 2 heat exchanger (6), a No. 2 hydrogen membrane separator (7) and a No. 1 electrochemical hydrogen pump H 2 Separation device (8), 3# compressor (9), 3# heat exchanger (10), 2# buffer tank (11), 3# hydrogen membrane separator (12), 4# heat exchanger (13), 1# CO 2 Membrane separator (14), no. 5 heat exchanger (15), no. 1 electrochemical hydrogen pump CO 2 A hydrogenation device (16), a No. 4 compressor (17), a No. 6 heat exchanger (18) and a No. 1 liquid separating tank (19);
the No. 1 compressor (1), the No. 1 heat exchanger (2) and the No. 1 buffer tank (3) are sequentially connected; the outlet of the No. 1 buffer tank (3) is connected with the inlet of the No. 1 hydrogen membrane separator (4), the permeation side of the No. 1 hydrogen membrane separator (4) is sequentially connected with the No. 2 compressor (5) and the No. 2 heat exchanger (6), the outlet of the No. 2 heat exchanger (6) is connected with the inlet of the No. 2 hydrogen membrane separator (7), and the No. 2 hydrogen membrane is separatedPermeate side of the reactor (7) and # 1 electrochemical hydrogen pump H 2 The inlet of the separating device (8) is connected; the permeation side of the No. 2 hydrogen membrane separator (7) is connected with the No. 1 buffer tank (3); no. 1 electrochemical hydrogen Pump H 2 The anode side outlet of the separation device (8) is sequentially connected with a No. 3 compressor (9), a No. 3 heat exchanger (10) and a No. 2 buffer tank (11); the outlet of the No. 2 buffer tank (11) is connected with the inlet of the No. 3 hydrogen membrane separator (12), and the retentate side of the No. 3 hydrogen membrane separator (12) is connected with the No. 1 CO 2 The inlet of the membrane separator (14) is connected; the permeation side of the No. 3 hydrogen membrane separator (12) is connected with a No. 4 heat exchanger (13), and the outlet of the No. 4 heat exchanger (13) is connected with a No. 1 electrochemical hydrogen pump CO 2 The anode inlet of the hydrogenation unit (16) is connected with the No. 1#CO 2 The permeation side of the membrane separator (14) is connected with a No. 5 heat exchanger (15), and the outlet of the No. 5 heat exchanger (15) is connected with a No. 1 electrochemical hydrogen pump CO 2 The cathode inlet of the hydrogenation device (16) is connected with the No. 1 electrochemical hydrogen pump CO 2 The anode outlet of the hydrogenation device (16) is sequentially connected with a No. 4 compressor (17), a No. 6 heat exchanger (18) and a No. 2 buffer tank (11), and a No. 1 electrochemical hydrogen pump CO 2 The cathode outlet of the hydrogenation device (16) is connected with a No. 1 liquid separating tank (19); the retentate side of the No. 1 hydrogen membrane separator (4) and No. 1 CO 2 The residual seepage sides of the membrane separators (14) are connected with a natural gas pipeline.
2. Use of the system of claim 1 for membrane separation of hydrogen-loaded natural gas coupled with electrochemical hydrogen pump for hydrogen and CO extraction 2 The hydrogenation process of preparing formic acid features that the hydrogen-doped natural gas has CH as main component 4 、H 2 、C 2 H 6 、CO 2 And C 3 H 8 The method comprises the steps of carrying out a first treatment on the surface of the Firstly, hydrogen-doped natural gas enters a No. 1 hydrogen membrane separator (4) to be enriched with H 2 H-rich on permeate side 2 The air flow enters a No. 2 hydrogen membrane separator (7) for H 2 Performing primary concentration, and enriching CH on the residual side 4 The gas flow returns to the natural gas pipeline to be continuously conveyed to a downstream natural gas end user; h-enriched permeate side of No. 2 hydrogen membrane separator (7) 2 The gas flow enters a No. 1 electrochemical hydrogen pump H 2 High-purity H for fuel cell automobile is prepared by separating device (8) 2 The product, the residual side returns to the No. 1 buffer tank (3) for recycling to be extractedHigh H 2 Recovery rate; no. 1 electrochemical hydrogen Pump H 2 The cathode side of the separation device (8) outputs high-purity hydrogen, and the dehydrogenation tail gas at the anode side sequentially enters a No. 3 hydrogen membrane separator (12) and a No. 1 CO after being compressed 2 Membrane separator (14) to obtain a H-enriched product 2 And is rich in CO 2 Gas flow and recovery of CH in dehydrogenation tail gas 4 The method comprises the steps of carrying out a first treatment on the surface of the Rich in H 2 And is rich in CO 2 The gas flows respectively enter the No. 1 electrochemical hydrogen pump CO 2 Anode and cathode of hydrogenation unit (16), under the drive of applied voltage, anode H 2 Dissociation to produce H + CO entering the surface of the cathode catalytic layer and the cathode through the proton exchange membrane and the buffer solution 2 React to generate formic acid, CO and H 2 O and H 2 The method comprises the steps of carrying out a first treatment on the surface of the The cathode gas-liquid phase mixture enters a No. 1 liquid separating tank (19), formic acid solution and fuel gas are obtained after flash evaporation separation, the fuel gas can enter a hydrogen pipe network, and the formic acid solution is conveyed to an external device of the boundary region.
3. The method according to claim 2, characterized in that it comprises in particular:
h in the hydrogen-doped natural gas 2 The concentration is more than 5mol%, the mixture is pressurized to 2.0-5.0 MPa by a No. 1 compressor (1), the mixture is cooled to 40-80 ℃ by a No. 1 heat exchanger (2), and enters a No. 1 buffer tank (3) to be mixed with circulating material flows from the retentate side of a No. 2 hydrogen membrane separator (7) in the No. 1 buffer tank (3), and enters a No. 1 hydrogen membrane separator (4) to be separated; the permeation side pressure of the No. 1 hydrogen membrane separator (4) is 0.1-0.5 MPa, hydrogen in the gas at the permeation side of the membrane is initially concentrated, the hydrogen is pressurized to 2.0-5.0 MPa by a No. 2 compressor (5), cooled to 40-80 ℃ by a No. 2 heat exchanger (6), and enters a No. 2 hydrogen membrane separator (7) for further concentration; the residual gas of the No. 1 hydrogen membrane separator (4) returns to the natural gas pipeline to be continuously conveyed to a downstream natural gas end user; the permeation side pressure of the No. 2 hydrogen membrane separator (7) is 0.1-0.5 MPa, and the gas on the permeation side of the membrane is concentrated to H 2 The concentration is more than 80mol percent, and enters a No. 1 electrochemical hydrogen pump H 2 Separating by a separating device (8) to obtain H on the cathode side 2 Purity of>99.97% CO purity<0.2ppm，CO 2 Purity of<2ppm，CH 4 Purity of<High purity H for 2ppm fuel cell automobile 2 A product; the residual gas of the No. 2 hydrogen membrane separator (7) returns to the No. 1 buffer tank (3) for circulation so as to improve H 2 Recovery rate; no. 1 electrochemical hydrogen Pump H 2 The dehydrogenation tail gas at the anode side of the separation device (8) is compressed to 2.0-5.0 MPa by a No. 3 compressor (9), cooled to 40-80 ℃ by a No. 3 heat exchanger (10), enters a No. 2 buffer tank (11) and is mixed with a stream cooled by a No. 6 heat exchanger (18); the mixed gas enters a No. 3 hydrogen membrane separator (12) to obtain H-enriched gas on the permeation side 2 The air flow is cooled to 25-35 ℃ by a No. 4 heat exchanger (13) and then enters a No. 1 electrochemical hydrogen pump CO 2 An anode of a hydrogenation unit (16); the residual gas of the No. 3 hydrogen membrane separator (12) enters No. 1#CO 2 A membrane separator (14) for obtaining CO-enriched at the permeate side 2 The air flow is cooled to 25-35 ℃ by a No. 5 heat exchanger (15) and then enters a No. 1 electrochemical hydrogen pump CO 2 A cathode of a hydrogenation unit (16); 1# CO 2 The gas on the permeate side of the membrane separator (14) returns to the natural gas pipeline to be continuously conveyed to a downstream natural gas end user; no. 1 electrochemical Hydrogen Pump CO 2 The external power supply of the hydrogenation device (16) adopts a constant voltage mode, the cathode potential range is 2.2-2.8V, and the catalyst is Ag/AgCl; under the action of an applied voltage, the No. 1 electrochemical hydrogen pump CO 2 Hydrogen on the anode side of the hydrogenation device (16) is dissociated into H + And pass through the proton exchange membrane and buffer solution to reach the cathode, and CO on the cathode side 2 The reaction is efficient to prepare formic acid; the anode outlet gas F is compressed to 2.0-5.0 MPa by a No. 4 compressor (17), enters a No. 6 heat exchanger (18) to be cooled to 40-80 ℃ and then enters a No. 2 buffer tank (11); and the cathode gas-liquid phase mixture I enters a No. 1 liquid separating tank (19), and formic acid solution and fuel gas are obtained after flash evaporation separation.
4. A method according to claim 2 or 3, wherein the hydrogen 1 membrane separator (4), the hydrogen 2 membrane separator (7), the hydrogen 3 membrane separator (12), the hydrogen 1 membrane separator (1) and the hydrogen 1 membrane separator (2) are arranged in the same order 2 The membrane structure used by the membrane separator (14) is a hollow fiber membrane or a flat membrane; the hollow fiber membrane or the flat membrane is an organic membrane.
5. A method according to claim 2 or 3, wherein the 1 st electric isChemical hydrogen pump H 2 The separation device (8) is a low-temperature electrochemical hydrogen pump, the adopted catalyst is a platinum noble metal catalyst or a non-noble metal catalyst, the adopted proton exchange membrane material is a perfluorosulfonic acid proton exchange membrane or a non-fluorine proton exchange membrane, and the adopted gas diffusion layer material is carbon paper.
6. A method according to claim 2 or claim 3 wherein the hydrogen content of the feed hydrogen-loaded natural gas is greater than 5.0mol%.
7. A method according to claim 2 or 3, characterized in that the # 1 compressor (1), # 2 compressor (5), # 3 compressor (9), # 4 compressor (17) employed in the hydrogen separation and recovery system is a reciprocating compressor, a centrifugal compressor, an axial compressor or a screw compressor.
8. A method according to claim 2 or 3, wherein the electrochemical hydrogen pump H # 1 2 The hydrogen content of the high-purity hydrogen obtained on the cathode side of the separation device (8) is more than or equal to 99.97mol percent.
9. A method according to claim 2 or 3, wherein the electrochemical hydrogen pump CO # 1 2 The proton exchange membrane material used by the hydrogenation device (16) is a perfluorosulfonic acid proton exchange membrane or a non-fluoroproton exchange membrane.
10. A method according to claim 2 or 3, wherein the electrochemical hydrogen pump CO # 1 2 CO of hydrogenation unit (16) 2 The raw material can be CO contained in the hydrogen-doped natural gas 2 CO trapped in the out-of-limit region may be 2 。
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